Nonvolatile memory device with multiple blocking layers and method of fabricating the same

ABSTRACT

A nonvolatile memory device with a blocking layer controlling the transfer of electric charges in a charge storage layer includes the blocking layer having a first blocking layer in contact with the charge storage layer and a second blocking layer over the first blocking layer, wherein the first blocking layer has a greater energy band gap than the second blocking layer and the second blocking layer has a greater permittivity than the first blocking layer.

CROSS-REFERENCE TO RELATED APPLICATIONS

The present application claims priority of Korean patent applicationnumber 10-2008-0040832, filed on Apr. 30, 2008, which is incorporatedherein by reference in its entirety.

BACKGROUND

The disclosure relates to a method of fabricating a semiconductordevice, and more particularly to a nonvolatile memory device and amethod of fabricating the same.

Nonvolatile memory devices are divided into a floating gate (FG) typeand a charge trap type depending on the type of the electric chargestorage layer. The floating gate type can keep electric charges into thefloating gate as a form of free charges, and the charge trap type cankeep electric charges in traps which are provided in the charge storagelayer. The floating gate type includes a dielectric layer betweencontrol gates. The dielectric layer may include a stack structure of anoxide layer, a nitride layer and an oxide layer, i.e., an ONO layer or ahigh k dielectric layer.

The typical charge trap type nonvolatile memory device may include aMANOS structure, as shown in FIG. 1A.

FIG. 1A illustrates a cross-sectional view of a charge trap typenonvolatile memory device with a typical metal/aluminumoxide/nitride/oxide/silicon (MANOS) structure.

Referring to FIG. 1A, the MANOS structure includes a silicon substrate11, a tunneling layer 12, a silicon nitride (Si₃N₄) layer 13, analuminum oxide layer 14 and a metal layer 15. The tunneling layer 12 mayinclude a silicon oxide layer.

The floating gate type nonvolatile memory device with an ONO structuremay have a structure as shown in FIG. 1B.

FIG. 1B illustrates a cross-sectional view of a typical floating gatetype nonvolatile memory device with an ONO structure. An isolation layer22 is formed over a substrate 21 having trenches. More particularity,the isolation layer 22 is formed to fill the trenches of the substrate31. A tunneling layer 23 and a floating gate 24 are sequentially formedover protruding portions of the substrate 21. Then, an ONO layer 25 anda control gate 26 are formed over the floating gate 24 and the isolationlayer 22 in sequence.

Referring to FIG. 1B, a substantial magnitude of capacitance may beensured since the ONO layer 25 and the control gate 26 are surroundingthe floating gate 24. Due to this structure, the coupling ratio of thedevice may be increased. However, in a highly integrated nonvolatilememory device having a line width of 40 nm or less, an interference Cbetween neighboring floating gates may occur. In order to overcome suchdrawbacks as interferences, the structure as shown in FIG. 1C may besuggested.

FIG. 1C illustrates a cross-sectional view of a floating gate typenonvolatile memory device with a typical inter poly dielectric (IPD)structure.

Referring to FIG. 1C, an isolation layer 32 is formed over a substrate31 having trenches. More particularity, the isolation layer 32 is formedto fill the trenches of the substrate 31. A tunneling layer 33 and afloating gate (FG) 34 are sequentially formed over protruding portionsof the substrate 31. The gap between neighboring floating gates 34 isfilled with the isolation layer 32. An IPD 35 and a control gate (CG) 36are sequentially formed over a planarized surface of the floating gate34 and the isolation layer 32.

The capacitance area of the structure as shown in FIG. 1C may bedecreased, when compared to the capacitance area of the structure asshown in FIG. 1A, since the IPD 35 and the control gate 36 are formedover the surface of the floating gate 34. Thus, the equivalent oxidethickness (EOT) of the IPD 35 should be decreased in order to increaseits coupling ratio. In order to increase the coupling ratio, it issuggested to use a high-k dielectric layer having a greater dielectricconstant than the ONO structure as an IPD layer.

However, since the silicon nitride layer (Si₃N₄) 13 is used as a chargestorage layer in the typical MANOS structure, the silicon nitride layer13 may not be removed. Furthermore, the low energy band gap of thealuminum oxide layer 14 that is used as a blocking layer and many trapsite formed in the aluminum oxide layer 14 deteriorate the dateretention characteristics of the nonvolatile memory devices.

Moreover, in the typical floating gate structure as shown in FIG. 1C,since most of the high-k dielectric layers have a low energy band-gapand many trap site, the device's speed characteristics in programmingand erasing operations and data retention characteristics aredeteriorated.

FIG. 2 is a graph illustrating the loss of electric charges in a dataretention mode with respect to a nonvolatile memory device having atypical MONOS structure.

Referring to FIG. 2, in the data retention mode, an energy band has aslight tilt. The tilt is caused by an internal field owing to electroncharges trapped in a charge storage layer. Thus, some of the electriccharges are lost in the data retention mode since the electric chargestrapped in the charge storage layer are drained off to the blockinglayer.

In general, when an electron having the highest trap level in thesilicon nitride layer is in a thermally excited state, the excitedelectron (e) transfers to the conduction band E_(C) of the siliconnitride layer.

At first, the electron (e) transferred to the conduction band is likelyto jump over the band offset (BO) {circle around (1)} since the bandoffset (BO) between the conduction bands of the silicon nitride layerand the aluminum oxide layer is small.

Then, the electron (e) that has been transferred to the conduction bandE_(C) of the silicon nitride layer is drained off through the many trapsT {circumflex over (2)}.

The above-mentioned loss of the electric charges may occur in floatinggates. That is, the electric charges stored in the floating gate may belost owing to the use of a high-k dielectric layer having a low energyband gap and many trap sites.

SUMMARY

In accordance with one or more embodiments, a nonvolatile memory devicewith a blocking layer controls the transfer of electric charges in acharge storage layer. The nonvolatile memory device includes theblocking layer having a first blocking layer in contact with the chargestorage layer and a second blocking layer over the first blocking layer,wherein the first blocking layer has a greater energy band gap than thesecond blocking layer, and the second blocking layer has a greaterpermittivity than the first blocking layer.

In accordance with one or more embodiments, there is provided a methodof fabricating a nonvolatile memory device. The method includes forminga tunneling layer over a first conductive layer, forming a chargestorage layer over the tunneling layer, forming a blocking layerincluding a first blocking layer and a second blocking layer, andforming a second conductive layer over the blocking layer, wherein thefirst blocking layer contacting the charge storage layer has a greaterenergy band gap than the second blocking layer formed over the firstblocking layer.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1A illustrates a cross-sectional view of a charge trap typenonvolatile memory device with a typical metal/aluminumoxide/nitride/oxide/silicon (MANOS) structure.

FIG. 1B illustrates a cross-sectional view of a typical floating gatetype nonvolatile memory device with an oxide/nitride/oxide (ONO)structure.

FIG. 1C illustrates a cross-sectional view of a floating gate typenonvolatile memory device with a typical inter poly dielectric (IPD)structure.

FIG. 2 is a graph illustrating the loss of electric charges in a dataretention mode with respect to a nonvolatile memory device having atypical MONOS structure.

FIG. 3A illustrates a cross-sectional view of a nonvolatile memorydevice structure in accordance with an embodiment.

FIG. 3B shows an energy band diagram with respect to a charge storagelayer and a blocking layer in accordance with the embodiment.

FIG. 4A illustrates a cross-sectional view of a nonvolatile memorydevice structure in accordance with another embodiment.

FIG. 4B shows an energy band diagram with respect to a charge storagelayer and a blocking layer in accordance with the another embodiment.

FIGS. 5A to 5E are cross-sectional views of the nonvolatile memorydevice in accordance with the embodiment.

FIGS. 6A to 6F are cross-sectional views of the nonvolatile memorydevice in accordance with the another embodiment.

FIG. 7A is a comparative graph showing flat band voltages (V_(FB)) ofthe nonvolatile memory device according to the another embodiment and atypical MANOS structure with respect to programming times.

FIG. 7B is a comparative graph showing flat band voltages (V_(FB)) ofthe nonvolatile memory device according to the another embodiment andthe typical MANOS structure with respect to erasing times.

FIG. 8 is a comparative graph showing data retention characteristics ofthe nonvolatile memory device according to the another embodiment andthe typical MANOS structure.

DESCRIPTION OF EMBODIMENTS

Nonvolatile memory devices in accordance with some embodiments arecapable of improving a speed characteristic of programming and erasingoperations and a data retention characteristic.

In nonvolatile memory devices including a blocking layer for preventinga transfer of electric charges stored in a charge storage layer, theblocking layer according to an embodiment is a compound of materialshaving different energy band gaps. The blocking layer may include ahigh-k dielectric layer having a high dielectric constant in order todecrease its equivalent oxide thickness (EOT). The high-k dielectriclayer having the high dielectric constant represents a layer formed of amaterial which has a dielectric constant greater than that of siliconoxide (SiO₂) or silicon nitride (Si₃N₄). Specifically, the highdielectric constant of the high-k dielectric layer is equal to orgreater than 9. The blocking layer also includes a material having agreater energy band gap than that of the high-k dielectric layer inorder to prevent a loss of electric charges of the charge storage layerdue to the low energy band gap and many trap sites of the high-kdielectric layer.

Therefore, the blocking layer in one or more embodiments includes amultilayer structure which is a stack of materials having differentenergy band gaps.

FIG. 3A illustrates a cross-sectional view of a nonvolatile memorydevice structure in accordance with an embodiment.

Referring to FIG. 3A, a tunneling layer 101 is formed over a firstconductive layer 100. A charge storage layer 102 is formed over thetunneling layer 101, and a blocking layer 103 is formed over the chargestorage layer 102. A second conductive layer 104 is formed over theblocking layer 103. Herein, when a layer is referred to as being“on/over” another layer or substrate, it can be directly on the otherlayer or substrate, or intervening layers may also be present. Inaddition, when a layer is referred to as being ‘between’ two layers, itcan be the only layer between the two layers, or one or more interveninglayers may also be present.

The first conductive layer 100 may include a silicon substrate, and thesilicon substrate may be doped with impurities such as a P-type impurityor N-type impurity. More particularly, the silicon substrate may bedoped with a P-type impurity such as boron (B). Furthermore, the firstconductive layer 100 may include a channel region, and a source regionand a drain region formed on both sides of the channel region.

The second conductive layer 104 may include a polysilicon layer or astack structure of a polysilicon layer and a metal layer. As an example,FIG. 3A illustrates a stack structure of a first metal layer 104A, apolysilicon layer 104B and a second metal layer 104C. In the stackstructure shown in FIG. 3A, the first metal layer 104A may include ametal layer having a high work function greater than a mid gap. Ingeneral, the work function of a material represents the energydifference between the Fermi level and vacuum level the material.Furthermore, the high work function greater than the mid gap means thata work function of the material is greater than a mid gap of silicon,wherein the mid gap of a material represents the difference in energylevel between the valence band and the conduction band of the material.Thus, the high work function greater than the mid gap has a range ofapproximately 4.0 eV to approximately 5.3 eV. The metal layer with ahigh work function within the above range may include one selected froma group consisting of Pt, Ru, TiN, WN, TaN, Ir, Mo, Co, Ni, NiSi,NiPtSi, NiCSi, CoSi, and a combination thereof. The first metal layer104A having the high work function contacts with the blocking layer 103,thus improving the leakage current characteristics of the blocking layer103. Furthermore, the polysilicon layer 104B in the stack structure isused as a control gate, and the second metal layer 104C may include alow resistance metal layer, such as tungsten (W), for decreasing theresistance of the control gate. Although it is not shown, a hard maskinsulation layer may be formed over the second metal layer 104.

The tunneling layer 101 may include a material having a greater energyband gap than those of the first conductive layer 100 and the chargestorage layer 102. More particularly, the tunneling layer 101 mayinclude an oxide layer such as a silicon oxide (SiO₂) layer or anoxynitride-containing layer such as a silicon oxynitride (SiON) layer.As described above, when the tunneling layer 101 has a large band gap,the electric charges programmed in the charge storage layer 102 cannotjump or transfer.

The charge storage layer 102 is used to trap electrons or holes injectedthrough the tunneling layer 101. Therefore, the charge storage layer 102may be referred to as a charge trap layer or a charge accumulatinglayer. The charge storage layer 102 may include a material containingnitride such as silicon nitride (Si₃N₄) in order to have a high densityof trap sites. Furthermore, the charge storage layer 102 may include apolysilicon layer. In general, when the charge storage layer 102 in adevice includes a silicon nitride layer, the device becomes a chargetrap type nonvolatile memory device, and when the charge storage layer102 in a device includes a polysilicon layer, the device becomes afloating type nonvolatile memory device. Hereinafter, the charge storagelayer 102 is regarded as including a silicon nitride layer for thepurpose of simplification, while the charge storage layer 102 mayinstead include a polysilicon layer.

While the electric charges that have transferred through the tunnelinglayer 101 are trapped in the charge storage layer 102, the blockinglayer 103 formed between the charge storage layer 102 and the secondconductive layer 104 is used as an insulation layer for preventing theelectric charges from transferring to the second conductive layer 104.Thus, the blocking layer 103 may include a high-k dielectric layerhaving a high permittivity in order to prevent the transfer of theelectric charges and decrease the EOT. However, since the high-kdielectric layer that is used as the blocking layer 103 has a low energyband gap and many trap sites, some loss of the electric charges in thecharge storage layer 102 may be inevitable when the blocking layer 103is in direct contact with the charge storage layer 102. That is, theelectric charges in the charge storage layer 102 may transfer to theblocking layer 103 due to the low energy band gap of the high-kdielectric layer that is used as the blocking layer 103. Thus, theelectric charges are trapped in the trap sites of the blocking layer103, and the loss of the electric charges in the charge storage layer102 is caused.

In order to prevent the loss of the electric charges in the chargestorage layer 102, the blocking layer 103 may include a first blockinglayer 103A in contact with the charge storage layer 102. Therefore, theblocking layer 103 may include the first blocking layer 103A forming aninterface by contacting with the charge storage layer 102 and a secondblocking layer 103B formed by using a high-k dielectric layer. In thisembodiment, the second blocking layer 103B may contact with the secondconductive layer 104.

The first blocking layer 103A is formed by using a dielectric layerhaving a greater energy band gap E_(g) than that of the second blockinglayer 103B in order to prevent the transfer of the electric charges inthe charge storage layer 102. The first blocking layer 103A having ahigh energy band gap has a low permittivity due to the high energy bandgap. Thus, the first blocking layer 103A has less trap sites than thesecond blocking layer 103B including the high-k dielectric layer.

When the first blocking layer 103A has a high energy band gap, the bandoffset value generated at the interface between the first blocking layer103A and the charge storage layer 102 may be high. The band offsetrepresents an energy difference between the conduction bands of twocontacting materials in an energy band diagram.

The first blocking layer 103A may include a material having a bandoffset greater than the band offset caused by contacting the secondblocking layer 103B and the charge storage layer 102. When an electricpotential barrier becomes high, the electric charges in the chargestorage layer 102 may not jump or transfer. Thus, jump or transfer ofthe electric charges in the charge storage layer 102 can be controlled,since the electric potential barrier becomes high when the value of theband offset is high. The band offset will be described in FIG. 3B.

Moreover, when the first blocking layer 103A has a low permittivity, theprobability of the electric charges being trapped in the first blockinglayer 103A may be decreased since the first blocking layer 103A has asmall number of trap sites. That is, the first blocking layer 103A has atrap density smaller than those of the second blocking layer 103B andthe charge storage layer 102.

When the second blocking layer 103B includes a high-k dielectric layer,the first blocking layer 103A may include a dielectric layer having agreater energy band gap than that of the high-k dielectric layer.

The high-k dielectric layer used as the second blocking layer 103B mayinclude MAlO, wherein M represents a metal, or DyScO includingdysprosium (Dy) and scandium (Sc). The M in MAlO may include oneselected from a group consisting of Hf, Zr, La, Gd, Y, Nd, Ce and Pr.Thus, the MAlO becomes one selected from a group consisting of HfAlO,ZrAlO, LaAlO, GdAlO, YAlO, NdAlO, CeAlO and PrAlO. The high-k dielectriclayers described herein have an energy band gap ranging fromapproximately 3 eV to approximately 6 eV. The second blocking layer 103Bmay include an aluminum oxide layer or a metal oxide layer, wherein themetal includes one selected from a group consisting of Hf, Zr, La, Gd,Y, Nd, Ce and Pr. In order to improve leakage current characteristics,the second blocking layer 103B may include MAlO, wherein M represents ametal, or DyScO including Dy and Sc.

The first blocking layer 103A may include an oxide layer or anoxynitride layer. The oxide layer and the oxynitride layer have a largeenergy band gap of approximately 9 eV. Thus, since the first blockinglayer 103A having the large energy band gap has a great value of bandoffset at the interface between the first blocking layer 103A and thecharge storage layer 102, transfer of the electric charges in the chargestorage layer 102 may be controlled.

The first blocking layer 103A has a thickness smaller than that of thesecond blocking layer 103B and that of the charge storage layer 102. Thefirst blocking layer 103A has a thickness ranging from approximately 20Å to approximately 50 Å. The second blocking layer 103B has a thicknessranging from approximately 100 Å to approximately 300 Å and the chargestorage layer 102 has a thickness ranging from approximately 50 Å toapproximately 200 Å.

FIG. 3B is a graph showing an energy band diagram between a chargestorage layer and a blocking layer in accordance with the embodiment.

Hereinafter, the graph of the MANOS structure in FIG. 2 and the graph ofthe embodiment in FIG. 3B will be compared.

In the MANOS structure as shown in FIG. 2, the charge storage layer is asilicon nitride (Si₃N₄) layer and the blocking layer is an aluminumoxide (Al₂O₃) layer. In the embodiment as shown in FIG. 3B, the chargestorage layer 102 includes the silicon nitride (Si₃N₄) layer, the firstblocking layer 103A includes the silicon oxide (SiO₂) layer and thesecond blocking layer 103B includes the HfAlO layer. The energy band gapof HfAlO is smaller than that of aluminum oxide Al₂O₃ since HfAlO isformed by adding hafnium Hf into Al₂O₃. The energy band gap of Al₂O₃ranges from approximately 6 eV to approximately 8.7 eV and the energyband gap of HfAlO ranges from approximately 4.5 eV to approximately 8eV. Furthermore, the energy band gap of the silicon nitride layer isapproximately 5.3 eV and the energy band gap of the silicon oxide layeris approximately 9 eV. The energy band gap of a material is an energylevel difference between the conduction band and the valance band of thematerial. Moreover, since the energy band gap of the material may changedepending upon formation circumstances, only approximate values havebeen disclosed.

Referring to FIGS. 2, 3A and 3B, when the charge storage layer 102contacts with the first blocking layer 103A, an electric potentialbarrier is generated according to the energy band gap difference betweenthe materials forming the charge storage layer 102 and the firstblocking layer 103A. The band offset BO1 between the conduction bands ofthe silicon nitride layer and the silicon oxide layer in FIG. 3B isgreater than the band offset BO between the conduction bands of thesilicon nitride layer and the aluminum oxide layer in FIG. 2.

As a result, the MANOS structure of the disclosed embodiment isdifferent from that shown in FIG. 2, even when an electron (e) stored inthe silicon nitride layer as the charge storage layer obtains someenergy by heating or other methods, the electron (e) cannot jump overthe high band offset {circle around (3)}. Thus, the data retentioncharacteristics of the nonvolatile memory device can be improved. Incontrast, with regard to the MANOS structure as shown in FIG. 2, anelectron ‘e’ in the silicon nitride layer is drained over the bandoffset BO {circle around (1)} since the band offset BO between theconduction bands of the silicon nitride layer and the aluminum oxidelayer is small.

Furthermore, the probability of electrons that have transferred to theconduction band Ec of the silicon nitride layer jumping out to thesilicon oxide layer {circle around (4)} can be decreased since thesilicon oxide layer has a low density of trap sites.

FIG. 4A illustrates a cross-sectional view of a nonvolatile memorydevice structure in accordance with another embodiment.

Referring to FIG. 4A, a tunneling layer 201 is formed over a firstconductive layer 200. A charge storage layer 202 is formed over thetunneling layer 201 and a blocking layer 203 is formed over the chargestorage layer 202. A second conductive layer 204 is formed over theblocking layer 203.

The first conductive layer 200 may include a silicon substrate and thesilicon substrate may be doped with impurities such as a P-type impurityor N-type impurity. More particularly, the silicon substrate may bedoped with a P-type impurity like boron (B). Furthermore, the firstconductive layer 200 may include a channel region, and a source regionand a drain region formed on both sides of the channel region.

The second conductive layer 204 may include a polysilicon layer, a stackstructure of a polysilicon layer and a metal layer or a stack structureof a first metal layer 204A, a polysilicon layer 204B and a second metallayer 204C, as shown in FIG. 4A. In the stack structure shown in FIG.4A, the first metal layer 204A may include a metal layer having a highwork function greater than a mid gap. In general, the work function of ametal represents the energy difference between the Fermi level and thevacuum level of the metal. Furthermore, the high work function greaterthan the mid gap means that a work function of a material is greaterthan a mid gap of silicon, wherein the mid gap represents the energylevel between the valence band and the conduction band. Thus, the highwork function greater than the mid gap has a range of approximately 4.0eV to approximately 5.3 eV. The metal layer with a high work functionhaving the above range may include one selected from a group consistingof Pt, Ru, TiN, WN, TaN, Ir, Mo, Co, Ni, NiSi, NiPtSi, NiCSi, CoSi, anda combination thereof. The first metal layer 204A having a high workfunction contacts with the blocking layer 203, thus improving theleakage current characteristics of the blocking layer 203. Furthermore,the polysilicon layer 204B in the stack structure is used as a controlgate, and the second metal layer 204C may include a tungsten layer as alow resistance metal layer for decreasing the resistance of the controlgate. Although it is not shown, a hard mask insulation layer may beformed over the second metal layer 204.

The tunneling layer 201 may include a material having a greater energyband gap than those of the first conductive layer 200 and the chargestorage layer 202. The tunneling layer 201 may include an oxide layersuch as a silicon oxide (SiO₂) layer or an oxynitride-containing layersuch as a silicon oxynitride (SiON) layer. As described above, when thetunneling layer 201 has a large band gap, the electric chargesprogrammed in the charge storage layer 202 cannot jump or transfer.

The charge storage layer 202 is used to trap electrons or holes injectedthrough the tunneling layer 201. Therefore, the charge storage layer 202may be referred to as a charge trap layer or a charge accumulatinglayer. The charge storage layer 202 may include a material containingnitride such as silicon nitride (Si₃N₄) in order to have a high densityof trap sites. Furthermore, the charge storage layer 202 may include apolysilicon layer. In general, when the charge storage layer 202 in adevice includes a silicon nitride layer, the device becomes a chargetrap type nonvolatile memory device, and when the charge storage layer202 in a device includes a polysilicon layer, the device becomes afloating type nonvolatile memory device. Hereinafter, the charge storagelayer 102 is regarded as including a silicon nitride layer for thepurpose of simplification, while the charge storage layer 102 mayinstead include a polysilicon layer.

While the electric charges that have transferred through the tunnelinglayer 201 are trapped in the charge storage layer 202, the blockinglayer 203 formed between the charge storage layer 202 and the secondconductive layer 204 is used as an insulation layer preventing theelectric charges from transferring to the second conductive layer 204.Thus, the blocking layer 203 may include a high-k dielectric layerhaving a high permittivity in order to prevent the transfer of theelectric charges and decrease the EOT. The high-k dielectric layerhaving the high dielectric constant represents a layer formed of amaterial which has a dielectric constant greater than that of siliconoxide (SiO₂) or silicon nitride (Si₃N₄). Specifically, the highdielectric constant of the high-k dielectric layer is equal to orgreater than 9. However, since the high-k dielectric layer that is usedas the blocking layer 203 has a low energy band gap and many trap sites,the loss of the electric charges in the charge storage layer 202 may beinevitable when the blocking layer 203 is in direct contact with thecharge storage layer 202. That is, the electric charges in the chargestorage layer 202 may transfer to the blocking layer 203 due to the lowenergy band gap of the high-k dielectric layer that is used as theblocking layer 203. Thus, the electric charges are trapped in the trapsites in the blocking layer 203, and the loss of the electric charges inthe charge storage layer 202 may be caused.

In order to prevent the loss of the electric charges in the chargestorage layer 202, the blocking layer 203 may include a first blockinglayer 203A in contact with the charge storage layer 202. Therefore, theblocking layer 203 may include the first blocking layer 203A that formsan interface by contacting with the charge storage layer 202, and asecond blocking layer 203B that may be formed with a high-k dielectriclayer. Furthermore, the blocking layer 203 may further include a thirdblocking layer 203C in order to increase its blocking characteristic atthe portion in contact with the second conductive layer 204.

The first blocking layer 203A is formed by using a dielectric layerhaving a greater energy band gap E_(g) than that of the second blockinglayer 203B in order to prevent the transfer of the electric charges inthe charge storage layer 202. The first blocking layer 203A having ahigh energy band gap has a low permittivity due to the high energy bandgap. Thus, the first blocking layer 203A has less trap sites than thesecond blocking layer 203B including the high-k dielectric layer.

When the first blocking layer 203A has a high energy band gap, the bandoffset value that is generated at the interface between the firstblocking layer 203A and the charge storage layer 202 may be high. Theband offset represents the energy difference between the conductionbands of two contacting materials in an energy band diagram.

The first blocking layer 203A may include a material having a bandoffset greater than the band offset generated by contacting the secondblocking layer 203B and the charge storage layer 202. In thisembodiment, the transfer of the electric charges can be controlled,since the electric potential barrier that blocks the electric charges inthe charge storage layer 202 from transferring is increased when thevalue of the band offset is high. The band offset will be describedlater in further detail with reference to FIG. 4B.

Moreover, when the first blocking layer 203A has a low permittivity, theprobability of the electric charges being trapped in the first blockinglayer 203A may be decreased since the first blocking layer 203A has asmall number of the trap sites. That is, the first blocking layer 203Ahas a trap density smaller than those of the second blocking layer 203Band the charge storage layer 202.

When the second blocking layer 203B includes a high-k dielectric layer,the first blocking layer 203A may include a dielectric layer having agreater energy band gap than that of the high-k dielectric layer.

The high-k dielectric layer used as the second blocking layer 203B mayinclude MAlO, wherein M represents a metal, or DyScO includingdysprosium (Dy) and scandium (Sc). The M in MAlO may include oneselected from a group consisting of Hf, Zr, La, Gd, Y, Nd, Ce and Pr.Thus, the MAlO may be, but not limited to, one selected from a groupconsisting of HfAlO, ZrAlO, LaAlO, GdAlO, YAlO, NdAlO, CeAlO and PrAlO.The high-k dielectric layers described herein have an energy band gapranging from approximately 3 eV to approximately 6 eV. The secondblocking layer 203B may include an aluminum oxide layer or a metal oxidelayer, wherein the metal includes one selected from a group consistingof Hf, Zr, La, Gd, Y, Nd, Ce and Pr. In order to improve leakagecurrent, the second blocking layer 203B may include MAlO, wherein Mrepresents a metal, or DyScO including Dy and Sc.

The first blocking layer 203A may include an oxide layer or anoxynitride layer. The oxide layer and the oxynitride layer have a largeenergy band gap, for instance, approximately 9 eV. Thus, since the firstblocking layer 203A having such a large energy band gap has a high bandoffset at the interface between the first blocking layer 203A and thecharge storage layer 202, the transfer of the electric charges in thecharge storage layer 202 can be controlled.

The first blocking layer 203A may have a thickness smaller than that ofthe second blocking layer 203B and that of the charge storage layer 202.The first blocking layer 203A has a thickness ranging from approximately20 Å to approximately 50 Å. The second blocking layer 203B has athickness ranging from approximately 100 Å to approximately 300 Å andthe charge storage layer 202 has a thickness ranging from approximately50 Å to approximately 200 Å.

The third blocking layer 203C may include a dielectric layer having alarge energy band gap and a lower permittivity than that of the secondblocking layer 203B. The loss of electric charges can be prevented whenthe third blocking layer 203C has a large energy band gap. Thus,although some electric charges in the charge storage layer 202 maytransfer to the first blocking layer 203A and the second blocking layer203B, the electric charges in the second blocking layer 203B can beprevented from transferring to the third blocking layer 203C as thethird blocking layer 203C has a greater energy band gap than that of thesecond blocking layer 203B.

The third blocking layer 203C may have an energy band gap as high asthat of the first blocking layer 203A or greater than that of the firstblocking layer 203A. The third blocking layer 203C may include a metaloxide layer such as an aluminum oxide Al₂O₃ layer. The energy band gapof Al₂O₃ ranges from approximately 6 eV to approximately 8.7 eV.

As described above, the another embodiment has the blocking layer havingthe stack structure of dielectric layers having different energy bandgaps. The blocking effect of the structure in accordance with theanother embodiment can be further increased when compared to the firstembodiment, since the energy band gaps of the first blocking layer 203Ain contact with the charge storage layer 202, and the third blockinglayer 203C in contact with the second conductive layer 203, are greaterthan the energy band gap of the second blocking layer 203B.

FIG. 4B is a graph showing an energy band diagram with respect to thecharge storage layer and the blocking layer in accordance with theanother embodiment.

The graph of the MANOS structure shown in FIG. 2 will be compared withthe graph of the another embodiment in FIG. 4B, as below.

In the MANOS structure as shown in FIG. 2, the charge storage layer isthe silicon nitride (Si₃N₄) layer and the blocking layer is the aluminumoxide (Al₂O₃) layer. In the another embodiment as shown in FIG. 4B, thecharge storage layer 202 includes the silicon nitride (Si₃N₄) layer, andthe first blocking layer 203A includes the silicon oxide (SiO₂) layer.Further, the second blocking layer 203B includes a HfAlO layer, and thethird blocking layer 203C includes an aluminum oxide (Al₂O₃) layer. Ingeneral, the energy band gap of HfAlO is smaller than that of aluminumoxide (Al₂O₃) since HfAlO is formed by adding hafnium (Hf) into Al₂O₃.The energy band gap of Al₂O₃ ranges from approximately 6 eV toapproximately 8.7 eV, and the energy band gap of HfAlO ranges fromapproximately 4.5 eV to approximately 8 eV. Furthermore, the energy bandgap of the silicon nitride layer is approximately 5.3 eV, and the energyband gap of the silicon oxide layer is approximately 9 eV. The energyband gap of a material is the energy level difference between theconduction band and the valance band of the material.

Referring to FIGS. 2 and 4B, when the charge storage layer 202 contactswith the first blocking layer 203A, an electric potential barrier isgenerated according to the energy band gap difference between thematerials forming the charge storage layer 202 and the first blockinglayer 203A.

The band offset BO2 between the conduction bands of the silicon nitridelayer and the silicon oxide layer in FIG. 4B is greater than the bandoffset BO between the conduction bands of the silicon nitride layer andthe aluminum oxide layer in FIG. 2.

Even when an electron (e) stored in the silicon nitride layer as thecharge storage layer obtains some energy by heating or other methods,the electron (e) is not capable of jumping over the high band offset BO2{circle around (5)}. Thus, data retention characteristics of thenonvolatile memory device can be improved.

In contrast, with regard to the MANOS structure as shown in FIG. 2, anelectron (e) in the silicon nitride layer may jump over the band offsetBO {circle around (1)} since the band offset BO between the conductionbands of the silicon nitride layer and the aluminum oxide layer issmall.

Furthermore, the probability of electrons that have transferred to theconduction band Ec of the silicon nitride layer being drained out to thesilicon oxide layer {circle around (6)} can be decreased since thesilicon oxide layer has a low density of trap sites.

Moreover, in accordance with the another embodiment, even when theelectric charges are trapped in the HfAlO layer as the second blockinglayer 203B, the trapped electric charges cannot jump over the bandoffset BO3 from a trap level since there is the band offset BO3 betweenthe HfAlO layer and the aluminum oxide layer. Thus, the loss of theelectric charges can be minimized as the blocking layer includes thethird blocking layer.

FIGS. 5A to 5E are cross-sectional views illustrating the nonvolatilememory device in accordance with the first embodiment.

Referring to FIG. 5A, a tunneling layer 43 having a predeterminedthickness is formed over a substrate 41 after performing an ionimplantation process on the substrate 41 and forming an isolation layer42 over the substrate 41. The isolation layer 42 may be formed by ashallow trench isolation (STI) process, and the ion implantation processincludes an ion implantation process for controlling a thresholdvoltage. The tunneling layer 43 may include an oxide layer or anoxynitride-containing layer. The tunneling layer may include a puresilicon oxide (SiO₂) layer or silicon oxynitride (SiON) layer.

A charge storage layer 44 is formed over the tunneling layer 43. Thecharge storage layer 44 may include a silicon nitride layer such as aSi₃N₄ layer or a polysilicon layer. The charge storage layer 44 has athickness ranging from approximately 50 Å to approximately 200 Å.

A blocking layer is formed over the charge storage layer 44 afterforming the charge storage layer 44 in order to cut off a currentbetween the charge storage layer 44 and a conductive layer to besubsequently formed. The blocking layer may include a first blockinglayer and a second blocking layer in accordance with the firstembodiment.

Referring to FIG. 5B, a first blocking layer 45 is formed over thecharge storage layer 44. The first blocking layer 45 has a thicknessranging from approximately 20 Å to approximately 50 Å, wherein thethickness is smaller than that of the charge storage layer 44. The firstblocking layer 45 may include an oxide layer or an oxynitride layer.

When the first blocking layer 45 includes an oxide layer, the firstblocking layer 45 may be formed by performing a radical oxidation methodthat is to oxidize the surface of the charge storage layer 44.Therefore, a portion of the charge storage layer 44 is oxidized, and theoxidized portion of the charge storage layer 44 becomes the firstblocking layer 45. Thus, the first blocking layer 45 is an oxide layer,and has a thickness ranging from approximately 20 Å to approximately 50Å.

Another method for forming the first blocking layer 45 is a chemicalvapor deposition (CVD) method, which can be employed to form the firstblocking layer 45 having a predetermined thickness uniformly over thecharge storage layer 44. When the CVD method is used for forming thefirst blocking layer 45, a portion of the charge storage layer 44 maynot be oxidized, and an oxide layer is directly formed over the chargestorage layer 44. The oxide layer formed by using the CVD method has athickness ranging from approximately 20 Å to approximately 50 Å.

The first blocking layer 45, forming an interface with the chargestorage layer 44, may be made of a material having a permittivitysmaller than that of a high-k dielectric layer that is used as a secondblocking layer 46. The first blocking layer 45 may include an oxidelayer. The oxide layer used as the first blocking layer 45 has less trapsites than the high-k dielectric layer and, thus, the oxide layer has alarge value of band offset. Thus, the oxide layer that is used as thefirst blocking layer 45 separates the second blocking layer 46 from thecharge storage layer 44.

The radical oxidation method for forming the first blocking layer 45includes a thermal radical oxidation process or a plasma radicaloxidation process. The thermal radical oxidation process is performed ata temperature ranging from approximately 600° C. to approximately 1,200°C. and a pressure ranging from approximately 1 mTorr to approximately100 Torr. The radical oxidation method may be implemented by performingan oxidizing method using active oxygen, for instance, by injecting ahydrogen gas (H₂) and oxygen gas (O₂) or injecting a deuterium gas D₂and oxygen gas O₂ at the same time in order to generate the activeoxygen. The plasma radical oxidation process is performed by using a gasone selected from a group consisting of a mixed gas of argon (Ar), H₂and O₂, a mixed gas of Ar and O₂, a mixed gas of helium (He), H₂ and O₂,a mixed gas of He and O₂, a mixed gas of H₂ and O₂, an O₂ gas and acombination thereof, wherein the gas is used as a plasma-producing gas.Furthermore, the plasma radical oxidation process is performed with amicro wave (MW) or a radio frequency (RF) used as a plasma source. Theplasma radical oxidation process is performed at a plasma power rangingfrom approximately 100 W to approximately 3,000 W. Furthermore, theplasma radical oxidation process is performed for a process time rangingfrom approximately 5 sec to approximately 600 sec, at a substratetemperature ranging from approximately 0° C. to approximately 600° C.and a flow rate of the plasma producing gas ranging from 5 sccm toapproximately 2,000 sccm.

Alternatively, since the first blocking layer 45 may include theoxynitride layer instead of the oxide layer, a nitridation process maybe applied in order to form the oxynitride layer. For example, an oxidelayer is formed by the radical oxidation process or the CVD method, andthen the nitridation process is additionally performed by using athermal nitridation method or a plasma nitridation process. The thermalnitridaiton process is performed at a temperature ranging fromapproximately 700° C. to approximately 1,000° C. and a gas atmosphere,wherein the gas may include N₂O, No or NH₃. The plasma nitridationprocess includes a direct plasma method for directly forming nitrogen(N) plasma and a remote plasma method for nitrifying the top surface ofthe target layer by supplying N radicals only after forming nitrogenplasma in a separate place. The plasma nitridation process is performedby using a gas one selected from a group consisting of a mixed gas of Arand nitrogen gas (N₂), a mixed gas of He and N₂, a mixed gas of xenongas (Xe) and N₂, N₂, a nitrogen monoxide gas (NO), a nitrous oxide gas(N₂O) and a combination thereof. Furthermore, the plasma nitridationprocess is performed with a MW or a RF used as a plasma source. Theplasma nitridation process is performed at a plasma power ranging fromapproximately 100 W to approximately 3,000 W. The plasma nitridationprocess is performed for a process time ranging from approximately 5 secto approximately 600 sec, at a substrate temperature ranging fromapproximately 0° C. to approximately 600° C. and at a flow rate of theplasma producing gas ranging from 5 sccm to approximately 2,000 sccm.

The above mentioned oxynitride layer also has an energy band gap greaterthan that of a high-k dielectric layer that is used as the secondblocking layer 46.

Referring to FIG. 5C, the second blocking layer 46 is formed over thefirst blocking layer 45 by using the high-k dielectric layer. The secondblocking layer 46 has a thickness ranging from approximately 100 Å toapproximately 300 Å. The second blocking layer 46 is formed by using analuminum-based metal oxide layer or DyScO including Dy and Sc, whereinthe metal is one selected from a group consisting of Hf, Zr, La, Gd, Y,Nd, Ce and Pr. For example, the aluminum-based oxide metal layer mayinclude one selected from a group consisting of HfAlO, ZrAlO, LaAlO,GdAlO, YAlO, NdAlO, CeAlO and PrAlO. The second blocking layer 46 isformed by using an atomic layer deposition (ALD) method or a CVD method.

The blocking layer is formed by the above mentioned processes. Theblocking layer includes the first blocking layer 45 and the secondblocking layer 46. The first blocking layer 45 is a layer forming theinterface with the charge storage layer 44, and the second blockinglayer 46 is a layer forming the interface with a subsequent conductivelayer. The second blocking layer 46 and the charge storage layer 44 maybe separated from each other by the first blocking layer 45, and ablocking effect may be obtained by the second blocking layer 46.

A post-treatment may be performed on the second blocking layer 46. Moreparticularly, a post deposition annealing (PDA) process as thepost-treatment may be performed on the second blocking layer 46 in orderto improve the quality of the high-k dielectric layer that is used asthe second blocking layer 46. The PDA process includes a furnace processor a rapid thermal process (RTP) and is performed at a temperatureranging from approximately 700° C. to approximately 1,000° C. and at agas atmosphere, wherein the gas may include N₂ or O₂. The blockingeffect of the second blocking layer 46 may be further increased by thePDA.

Referring to FIG. 5D, a first metal layer 47, a polysilicon layer 48 anda second metal layer 49 are sequentially formed over the second blockinglayer 46. The first metal layer 47 is formed by using a material tocontrol leakage current of the second blocking layer 46 and the materialis a metal having a high work function. The first metal layer 47 with ahigh work function greater than a mid gap may include one selected froma group consisting of Pt, Ru, TiN, WN, TaN, Ir, Mo, Co, Ni, NiSi,NiPtSi, NiCSi, CoSi, and a combination thereof. The first metal layer 47has a thickness ranging from approximately 50 Å to approximately 200 Å.

The polysilicon layer 48 is used as a control gate, and the second metallayer 49 may include a low resistance metal layer, such as tungsten (W),for decreasing resistance of the control gate. Although it is not shown,a barrier metal layer may be formed between the polysilicon layer 48 andthe second metal layer 47 in order to prevent interactive diffusionbetween the polysilicon layer 48 and the second metal layer 47.

A hard mask insulation layer 50 is formed over the second metal layer49. The hard mask insulation layer 50 is used as an etch barrier duringa subsequent etching process. The hard mask insulation layer 50 mayinclude a nitride layer.

Referring to FIG. 5E, the hard mask insulation layer 50, the secondmetal layer 49, the polysilicon layer 48, the first metal layer 47, thesecond blocking layer 46, the first blocking layer 45 and the chargestorage layer 44 are sequentially etched. Thus, a hard mask insulationpattern 50A, a second metal pattern 49A, a polysilicon pattern 48A, afirst metal pattern 47A, a second blocking pattern 46A, a first blockingpattern 45A and a charge storage pattern 44A are formed.

In the described structure, when the charge storage pattern 44A in adevice includes a silicon nitride layer, the device becomes a chargetrap type nonvolatile memory device, and when the charge storage pattern44A in a device includes a polysilicon layer, the device becomes afloating type nonvolatile memory device.

FIGS. 6A to 6F are cross-sectional views illustrating the nonvolatilememory device in accordance with the another embodiment.

Referring to FIG. 6A, a tunneling layer 53 having a predeterminedthickness is formed over a substrate 51 after performing an ionimplantation process on the substrate 51 and forming an isolation layer52 over the substrate 51. The isolation layer 52 is formed by a shallowtrench isolation (STI) process, and the ion implantation processincludes an ion implantation process for controlling a thresholdvoltage. The tunneling layer 53 may include an oxide layer or anoxynitride containing layer. The tunneling layer may include a puresilicon oxide (SiO₂) layer or silicon oxynitride (SiON) layer.

A charge storage layer 54 is formed over the tunneling layer 53. Thecharge storage layer 54 may include a silicon nitride layer such as aSi₃N₄ layer. The charge storage layer 54 has a thickness ranging fromapproximately 50 Å to approximately 200 Å.

A blocking layer is formed over the charge storage layer 54 afterforming the charge storage layer 54 in order to cut off a currentbetween the charge storage layer 54 and a conductive layer subsequentlyformed. Referring to FIG. 6B, a first blocking layer 55 is formed overthe charge storage layer 54. The first blocking layer 55 has a thicknessranging from approximately 20 Å to approximately 50 Å, wherein thethickness is smaller than that of the charge storage layer 54. The firstblocking layer 55 may include an oxide layer or an oxynitride layer.

When the first blocking layer 55 includes the oxide layer, the firstblocking layer 55 is formed by performing a radical oxidation methodoxidizing a surface of the charge storage layer 54. Therefore, a portionof the charge storage layer 54 is oxidized and the oxidized portion ofthe charge storage layer 54 becomes the first blocking layer 55. Thus,the first blocking layer 55 is the oxide layer and has a thicknessranging from approximately 20 Å to approximately 50 Å.

Another method for forming the first blocking layer 55 is a chemicalvapor deposition (CVD) method for forming the first blocking layer 55having a predetermined thickness uniformly over the charge storage layer54. When the CVD method is used for forming the first blocking layer 55,a portion of the charge storage layer 54 may not be oxidized and anoxide layer is directly formed over the charge storage layer 54. Theoxide layer formed by using the CVD method has a thickness ranging ofapproximately 20 Å to approximately 50 Å.

The first blocking layer 55, forming an interface between the chargestorage layer 54, may be made of a material having a permittivitysmaller than that of the high-k dielectric layer that is used as asecond blocking layer 56. The first blocking layer 55 may include anoxide layer. The oxide layer that is used as the first blocking layer 55has less trap sites than the high-k dielectric layer and, thus, theoxide layer has a large value of band offset. Thus, the oxide layer thatis used as the first blocking layer 55 separates the second blockinglayer 56 from the charge storage layer 54.

The radical oxidation method for forming the first blocking layer 55includes a thermal radical oxidation process or a plasma radicaloxidation process. The thermal radical oxidation process is performed ata temperature ranging from approximately 600° C. to approximately 1,200°C. and a pressure ranging from approximately 1 mTorr to approximately100 Torr. The radical oxidation method can be implemented by performingan oxidizing method using active oxygen, for instance, by injecting ahydrogen gas H₂ and oxygen gas O₂ or injecting a deuterium gas D₂ andoxygen gas O₂ at the same time in order to generate the active oxygen.The plasma radical oxidation process is performed by using a gas oneselected from a group consisting of a mixed gas of argon (Ar), H₂ andO₂, a mixed gas of Ar and O₂, a mixed gas of helium (He), H₂ and O₂, amixed gas of He and O₂, a mixed gas of H₂ and O₂, an O₂ gas and acombination thereof, wherein the gas is used as a plasma producing gas.Furthermore, the plasma radical oxidation process is performed with amicro wave (MW) or a radio frequency (RF) used as a plasma source. Theplasma radical oxidation process is performed at a plasma power rangingfrom approximately 100 W to approximately 3,000 W. Furthermore, theplasma radical oxidation process is performed for a process time rangingfrom approximately 5 sec to approximately 600 sec, at a substratetemperature ranging from approximately 0° C. to approximately 600° C.and at a flow rate of the plasma producing gas ranging from 5 sccm toapproximately 2,000 sccm.

Alternatively, since the first blocking layer 55 may include anoxynitride layer instead of the oxide layer, a nitridation process maybe applied in order to form the oxynitride layer. For example, the oxidelayer is formed by the radical oxidation process or the CVD method, andthen the nitridation process is additionally performed by using athermal nitridation method or a plasma nitridation process. The thermalnitridaiton process is performed at a temperature ranging fromapproximately 700° C. to approximately 1,000° C. and a gas atmosphere,wherein the gas may include N₂O, No or NH₃. The plasma nitridationprocess include a direct plasma method for directly forming nitrogen (N)plasma and a remote plasma method for nitrifying the top surface of thetarget layer by supplying N radicals only, after forming the nitrogenplasma in a separate place. The plasma nitridation process is performedby using a gas one selected from a group consisting of a mixed gas of Arand nitrogen gas (N₂), a mixed gas of He and N₂, a mixed gas of xenongas (Xe) and N₂, N₂, a nitrogen monoxide gas (NO), a nitrous oxide gas(N₂O) and a combination thereof. Furthermore, the plasma nitridationprocess is performed with a MW or a RF used as a plasma source. Theplasma nitridation process is performed at a plasma power ranging fromapproximately 100 W to approximately 3,000 W. The plasma nitridationprocess is performed for a process time ranging from approximately 5 secto approximately 600 sec, at a substrate temperature ranging fromapproximately 0° C. to approximately 600° C. and at a flow rate of theplasma producing gas ranging from 5 sccm to approximately 2,000 sccm.

The above mentioned oxynitride layer also has an energy band gap greaterthan that of the high-k dielectric layer used as the second blockinglayer 56.

Referring to FIG. 6C, the second blocking layer 56 is formed over thefirst blocking layer 55 by using the high-k dielectric layer. The secondblocking layer 56 has a thickness ranging from approximately 100 Å toapproximately 300 Å. The second blocking layer 56 is formed by using analuminum-based metal oxide layer or DyScO including Dy and Sc, whereinthe metal is one selected from a group consisting of Hf, Zr, La, Gd, Y,Nd, Ce and Pr. For example, the aluminum-based oxide metal layer mayinclude one selected from a group consisting of HfAlO, ZrAlO, LaAlO,GdAlO, YAlO, NdAlO, CeAlO and PrAlO. The second blocking layer 56 isformed by using an ALD method or a CVD method.

The first blocking layer 55 is a layer forming an interface with thecharge storage layer 54 and the second blocking layer 56 is a layerforming an interface with a subsequent conductive layer. The secondblocking layer 56 and the charge storage layer 54 can be separated bythe first blocking layer 55 and a blocking effect can be obtained by thesecond blocking layer 56.

A post-treatment may be performed on the second blocking layer 56. Moreparticularly, a post deposition annealing (PDA) process as thepost-treatment may be performed on the second blocking layer 56 in orderto improve the quality of the high-k dielectric layer used as the secondblocking layer 56. The PDA process includes a furnace process or a rapidthermal process (RTP) and is performed at a temperature ranging fromapproximately 700° C. to approximately 1,000° C. and at a gasatmosphere, wherein the gas may include N₂ or O₂. The blocking effect ofthe second blocking layer 56 can be further increased by the PDA.

Referring to FIG. 6D, a third blocking layer 57 is formed over thesecond blocking layer 56. The third blocking layer 57 may include adielectric layer, wherein the dielectric layer has a large energy bandgap and a lower permittivity than that of the second blocking layer 56.Thus, the loss of the electric charges can be further prevented sincethe third blocking layer 57 has the large energy band gap. Thus,although some electric charges in the charge storage layer 54 transferto the first blocking layer 55 and the second blocking layer 56, theelectric charges in the second blocking layer 56 cannot transfer to thethird blocking layer 57 as the third blocking layer 57 has a greaterenergy band gap than that of the second blocking layer 56.

The third blocking layer 57 may have an energy band gap as high as thatof the first blocking layer 55 or greater than that of the firstblocking layer 55. The third blocking layer 57 may include a metal oxidelayer such as an aluminum oxide Al₂O₃ layer. The energy band gap ofAl₂O₃ ranges from approximately 6 eV to approximately 8.7 eV.

Referring to FIG. 6E, a first metal layer 58, a polysilicon layer 59 anda second metal layer 60 are sequentially formed over the third blockinglayer 57. The first metal layer 58 is formed by using a material tocontrol leakage current of the second blocking layer 56 and the thirdblocking layer 57 and the material has a high work function. The firstmetal layer 58 with the high work function greater than a mid gap mayinclude one selected from a group consisting of Pt, Ru, TiN, WN, TaN,Ir, Mo, Co, Ni, NiSi, NiPtSi, NiCSi, CoSi, and a combination thereof.The first metal layer 58 has a thickness ranging from approximately 50 Åto approximately 200 Å.

The polysilicon layer 59 is used as a control gate and the second metallayer 60 may include a low resistance metal layer, such as tungsten (W),for decreasing resistance of the control gate. Although it is not shown,a barrier metal layer may be formed between the polysilicon layer 59 andthe second metal layer 60 in order to prevent interactive diffusionbetween the polysilicon layer 59 and the second metal layer 60.

A hard mask insulation layer 61 is formed over the second metal layer60. The hard mask insulation layer 61 is used as an etch barrier duringa subsequent etching process. The hard mask insulation layer 61 mayinclude a nitride layer.

Referring to FIG. 6F, the hard mask insulation layer 61, the secondmetal layer 60, the polysilicon layer 59, the first metal layer 58, thethird blocking layer 57, the second blocking layer 56, the firstblocking layer 55 and the charge storage layer 54 are sequentiallyetched. Thus, a hard mask insulation pattern 61A, a second metal pattern60A, a polysilicon pattern 59A, a first metal pattern 58A, a thirdblocking pattern 57A, a second blocking pattern 56A, a first blockingpattern 55A and a charge storage pattern 54A are formed.

In the described structure, when the charge storage pattern 54A in adevice includes a silicon nitride layer, the device becomes a chargetrap type nonvolatile memory device, and when the charge storage pattern54A in a device includes a polysilicon layer, the device becomes afloating type nonvolatile memory device.

FIG. 7A is a comparative graph showing the flat band voltages (V_(FB))of the nonvolatile memory device according to the another embodiment andthe typical MANOS structure with respect to programming times. TheX-axis represents the programming time and the Y-axis represents theflat band voltage V_(FB). A silicon oxide layer is used as the tunnelinglayer, a silicon nitride layer is used as the charge storage layer and astack structure of SiO₂, HfAlO and Al₂O₃ is used as the blocking layerin accordance with the another embodiment as shown in FIG. 7A. A siliconoxide layer is used as the tunneling layer, a silicon nitride layer isused as the charge storage layer and an Al₂O₃ layer is used as theblocking layer in accordance with the typical MANOS structure.

Referring to FIG. 7A, with respect to a same programming time, the flatband voltage V_(FB) of the another embodiment shows a different valuefrom that of the typical MANOS structure due to the difference in thetype of the blocking layers. However, the slope of the flat bandvoltages V_(FB) of the another embodiment is similar to that of thetypical MANOS structure. Thus, it can be seen that the programming timeof the another embodiment is similar to that of the typical MANOSstructure.

FIG. 7B is a comparative graph showing the flat band voltages (V_(FB))of the nonvolatile memory device according to the another embodiment andthe typical MANOS structure with respect to erasing times. The X-axisrepresents the erasing time and the Y-axis represents the flat bandvoltage V_(FB). A silicon oxide layer is used as the tunneling layer, asilicon nitride layer is used as the charge storage layer and a stackstructure of SiO₂, HfAlO and Al₂O₃ is used as the blocking layer inaccordance with the another embodiment as shown in FIG. 7B. A siliconoxide layer is used as the tunneling layer, a silicon nitride layer isused as the charge storage layer and an Al₂O₃ layer is used as theblocking layer in accordance with the typical MANOS structure.

It can be seen from FIG. 7B that the V_(FB) of the another embodimentusing the stack structure of SiO₂, HfAlO and Al₂O₃ as the blocking layeris smaller than the V_(FB) of the typical MANOS structure using only theAl₂O₃ layer as the blocking layer, with respect to a same erasing time.Based on the above result, it can be seen that when the stack structureof SiO₂, HfAlO and Al₂O₃ is used as the blocking layer, the erasingvoltage can be further decreased for the same erasing time. Furthermore,it also means that when the same erasing voltage is applied, the erasingtime can be further decreased.

FIG. 8 is a comparative graph showing the data retention characteristicsof the nonvolatile memory device according to the another embodiment andthe typical MANOS structure.

Referring to FIG. 8, with regard to programming statement P, the flatband voltage change (ΔV_(FB)) for approximately 1,000 sec isapproximately 1.25 V and, with regard to erasing statement E, the flatband voltage change (ΔV_(FB)) for approximately 1,000 sec is less thanapproximately 0.1 V in accordance with the another embodiment.

Referring further to FIG. 8, with regard to programming statement P, theflat band voltage change ΔV_(FB) for approximately 1,000 sec isapproximately 2.25 V and, with regard to erasing statement E, the flatband voltage change ΔV_(FB) for approximately 1,000 sec is less thanapproximately 0.1 V.

As such, it can be seen from FIG. 8 that the change of the V_(FB) of thedevice in accordance with the another embodiment is smaller than that inaccordance with the typical MANOS structure with regard to programmingstatement P with the passage of time. Furthermore, the flat band voltagein accordance with the another embodiment is much smaller than that inaccordance with the typical MANOS structure with the same passage oftime.

Referring to FIG. 8, it can be confirmed that the nonvolatile memorydevice in accordance with embodiments disclosed in the presentapplication has superior data retention characteristics.

According to the results in the above-described FIGS. 7A to 8,embodiments disclosed in the present application can improve programmingand erasing characteristics because the blocking layer is formed asmultiple layers such as stacked layers of SiO₂, HfAlO and Al₂O₃, insteadof using a monolayer such as an Al₂O₃ layer or a high-k dielectriclayer. Furthermore, embodiments can have superior data retentioncharacteristics to those of the typical MANOS structure and a typicalfloating gate type.

Further, although the results as shown in FIGS. 7A to 8 are obtained byusing the blocking layer as the stack structure of SiO₂, HfAlO andAl₂O₃, excellent programming and erasing characteristics and dataretention characteristics similar to those shown in FIGS. 7A to 8 can bealso obtained by using a stack structure of SiO₂ and HfAlO as theblocking layer.

As described above, in accordance with one or more embodiments, sincethe blocking layer is formed by using one selected from a groupconsisting of a stack structure of a high-k dielectric layer and anoxide layer, a stack structure of a high-k dielectric layer and anoxynitride layer, a stack structure of an aluminum oxide layer, a high-kdielectric layer and an oxide layer and a stack structure of aluminumoxide layer, a high-k dielectric layer and an oxynitride layer, userscan obtain improved programming and erasing characteristics and dataretention characteristics.

Reference numerals 101, 102, 103A, 103B, 104A, 104B and 104C in thedevice in FIG. 3A respectively correspond to reference numerals 43, 44,45, 46, 47, 48 and 49 in the device in FIG. 5E. Furthermore, referencenumerals 201, 202, 203A, 203B, 203C, 204A, 204B and 204C in the devicein FIG. 4A are respectively corresponding to reference numerals 53, 54A,55A, 56A, 57A, 58A, 59A, 60A in the device shown in FIG. 6F. Also, thedevices shown in FIGS. 3A and 4A are merely illustrated with distinctivefeatures for the purpose of simplification. Although FIGS. 5A to 5E andFIGS. 6A to 6F illustrate with all of the progress of the processes, thepatterning of the numerals 43 and 53 is omitted.

While embodiments have been described, the above embodiments areillustrative and not limitative. It will be apparent to those skilled inthe art that various changes and modifications may be made withoutdeparting from the spirit and scope of what is defined in the followingclaims.

1. A nonvolatile memory device with a blocking layer controllingtransfer of electric charges in a charge storage layer, the devicecomprising: the blocking layer having a first blocking layer in contactwith the charge storage layer and a second blocking layer over the firstblocking layer, wherein the first blocking layer has a greater energyband gap than the second blocking layer and the second blocking layerhas a greater permittivity than the first blocking layer.
 2. The deviceof claim 1, wherein the energy band gap of the first blocking layer isgreater than that of the charge storage layer.
 3. The device of claim 1,wherein the first blocking layer has a lower density of trap sites thanthe second blocking layer.
 4. The device of claim 1, wherein the firstblocking layer includes an silicon oxide (SiO₂) layer or a siliconoxynitride (SiON) layer.
 5. The device of claim 4, wherein the secondblocking layer includes one selected from the group consisting of HfAlO,ZrAlO, LaAlO, DyScO, GdAlO, YAlO, NdAlO, CeAlO and PrAlO.
 6. The deviceof claim 1, wherein the charge storage layer includes a silicon nitridelayer or a polysilicon layer.
 7. The device of claim 1, furthercomprising a metal layer formed over the blocking layer, the metal layerhaving a higher work function than a mid gap of silicon.
 8. The deviceof claim 7, wherein the metal layer includes one selected from the groupconsisting of Pt, Ru, TiN, WN, TaN, Ir, Mo, Co, Ni, NiSi, NiPtSi, NiCSi,CoSi, and a combination thereof.
 9. The device of claim 1, wherein theblocking layer further includes a third blocking layer formed over thesecond blocking layer, and wherein the third blocking layer has a lowerpermittivity and a greater energy band gap than those of the secondblocking layer.
 10. The device of claim 9, wherein the third blockingincludes a metal oxide layer.
 11. The device of claim 9, wherein thethird blocking includes an aluminum oxide (Al₂O₃) layer.
 12. A methodfor fabricating a nonvolatile memory device, the method comprising:forming a tunneling layer over a first conductive layer; forming acharge storage layer over the tunneling layer; forming a blocking layerincluding a first blocking layer and a second blocking layer; andforming a second conductive layer over the blocking layer, wherein thefirst blocking layer contacting the charge storage layer has a greaterenergy band gap than the second blocking layer formed over the firstblocking layer.
 13. The method of claim 12, wherein the second blockinglayer includes a high-k dielectric layer having a greater permittivitythan the first blocking layer.
 14. The method of claim 12, wherein thefirst blocking layer includes a dielectric layer having a greater energyband gap than the charge storage layer.
 15. The method of claim 12,wherein the dielectric layer has a lower density of trap sites than thesecond blocking layer.
 16. The method for claim 12, wherein the firstblocking layer includes an oxide layer or an oxynitride layer.
 17. Themethod of claim 12, wherein the first blocking layer includes a siliconoxide (SiO₂) layer or a silicon oxynitride layer (SiON).
 18. The methodof claim 12, wherein the second blocking layer includes one selectedfrom the group consisting of HfAlO, ZrAlO, LaAlO, DyScO, GdAlO, YAlO,NdAlO, CeAlO and PrAlO.
 19. The method of claim 12, wherein the chargestorage layer includes a silicon nitride layer or a polysilicon layer.20. The method of claim 12, wherein the first blocking layer is formedby oxidizing a portion of the charge storage layer.
 21. The method ofclaim 20, wherein the oxidizing of the portion of the charge storagelayer is performed by using a radical oxidation method.
 22. The methodof claim 12, wherein the first blocking layer is formed by oxidizing aportion of the charge storage layer and nitriding the oxidized portion.23. The method of claim 22, wherein the nitridation is performed byusing a thermal nitridation process or a plasma nitridation process. 24.The method of claim 12, wherein the second conductive layer comprises astack structure including a first metal layer having a work functiongreater than a mid gap of silicon.
 25. The method of claim 24, whereinthe first metal layer comprises one selected from the group consistingof Pt, Ru, TiN, WN, TaN, Ir, Mo, Co, Ni, NiSi, NiPtSi, NiCSi, CoSi, anda combination thereof.
 26. The method of claim 24, wherein the stackstructure comprises a polysilicon layer and a second metal layer formedover the first metal layer.
 27. The method of claim 12, furthercomprising forming a third blocking layer over the second blockinglayer, wherein the third blocking layer has a lower permittivity and agreater energy band gap than those of the second blocking layer.
 28. Themethod of claim 27, wherein the third blocking layer comprises a metaloxide layer.
 29. The method of claim 27, wherein the third blockinglayer comprises an aluminum oxide (Al₂O₃) layer.